Robert Kruk

Inkjet Printed, High Mobility Inorganic-Oxide Field Effect Transistors Processed at Room Temperature

Printed electronics (PE) represents any electronic devices, components or circuits that can be processed using modern-day printing techniques. Field-effect transistors (FETs) and logics are being printed with intended applications requiring simple circuitry on large, flexible (e.g., polymer) substrates for low-cost and disposable electronics. Although organic materials have commonly been chosen for their easy printability and low temperature processability, high quality inorganic oxide-semiconductors are also being considered recently. The intrinsic mobility of the inorganic semiconductors are always by far superior than the organic ones; however, the commonly expressed reservations against the inorganic-based printed electronics are due to major issues, such as high processing temperatures and their incompatibility with solution-processing. Here we show a possibility to circumvent these difficulties and demonstrate a room-temperature processed and inkjet printed inorganic-oxide FET where the transistor channel is composed of an interconnected nanoparticle network and a solid polymer electrolyte serves as the dielectric. Even an extremely conservative estimation of the field-effect mobility of such a device yields a value of 0.8 cm(2)/(V s), which is still exceptionally large for a room temperature processed and printed transistor from inorganic materials.

Electrical resistivity of nanocrystalline Al-doped zinc oxide films as a function of Al content and the degree of its segregation at the grain boundaries

Highly transparent and conducting Al-doped ZnO (AZO) films are prepared via sol-gel method with a broad range of nominal Al-doping. The film porosity and morphology is determined by the rate of temperature ramping during the drying of the gel phase. The minimum resistivity is observed to occur around 1.5–2 at. % Al-doped films, irrespective of the morphology and microstructure. It is found by local chemical analysis that Al tends to segregate at the grain boundaries and above a critical concentration, the segregated Al starts to dominate the electronic transport in nanocrystalline AZO. The optical measurements corroborate these findings showing a systematic increase in carrier density only up to 1.5–2 at. % Al-doping. It is concluded that the presence of the resistivity minimum is not merely determined by a solubility limit but is a result of the interplay between the changing carrier concentration and carrier scattering at the segregated Al.

A General Route toward Complete Room Temperature Processing of Printed and High Performance Oxide Electronics

Critical prerequisites for solution-processed/printed field-effect transistors (FETs) and logics are excellent electrical performance including high charge carrier mobility, reliability, high environmental stability and low/preferably room temperature processing. Oxide semiconductors can often fulfill all the above criteria, sometimes even with better promise than their organic counterparts, except for their high process temperature requirement. The need for high annealing/curing temperatures renders oxide FETs rather incompatible to inexpensive, flexible substrates, which are commonly used for high-throughput and roll-to-roll additive manufacturing techniques, such as printing. To overcome this serious limitation, here we demonstrate an alternative approach that enables completely room-temperature processing of printed oxide FETs with device mobility as large as 12.5 cm(2)/(V s). The key aspect of the present concept is a chemically controlled curing process of the printed nanoparticle ink that provides surprisingly dense thin films and excellent interparticle electrical contacts. In order to demonstrate the versatility of this approach, both n-type (In2O3) and p-type (Cu2O) oxide semiconductor nanoparticle dispersions are prepared to fabricate, inkjet printed and completely room temperature processed, all-oxide complementary metal oxide semiconductor (CMOS) invertors that can display significant signal gain (∼18) at a supply voltage of only 1.5 V.

The interplay of iron(II) spin transition and polymorphism

The mononuclear compound (1) [Fe(II)(L)(2)](BF(4))(2) (L = 4-ethynyl-2,6-bis(pyrazol-1-yl)pyridine) was prepared and structurally as well as magnetically characterised. The crystallisation revealed the formation of two polymorphs--the orthorhombic 1A and the tetragonal form 1B. A third, intermediate phase 1C was found exhibiting a different orthorhombic space group. Reversibility of the phase transition between 1A and 1C was studied by variable-temperature single-crystal and powder X-ray diffraction studies, while an irreversible phase transition was observed for the transition of 1B→1C. The magnetic studies show that the 1A↔1C transition is accompanied by a very abrupt spin transition (ST) with 8 K hysteresis width (T(1/2)(↓) = 337 K, T(1/2)(↑) = 345 K). The ST was confirmed by Mössbauer spectroscopy as well as by DSC studies. In contrast, the 1B polymorph remained low-spin up to 420 K. In conclusion, a full cycle of intertwined phase- and spin-conversions of three polymorphs could be proven following the general scheme 1B→1C↔1A.

Intercalation‐Driven Reversible Control of Magnetism in Bulk Ferromagnets

An extension in magnetoelectric effects is proposed to include reversible chemistry-controlled magnetization variations. This ion-intercalation-driven magnetic control can be fully reversible and pertinent to bulk material volumes. The concept is demonstrated for ferromagnetic iron oxide where the intercalated lithium ions cause valence change and partial redistribution of Fe(3+) cations yielding a large and fully reversible change in magnetization at room temperature.

Evidence for enhanced ferromagnetism in an iron-based nanoglass

The possibility to synthesize bulk amorphous materials with an internal nanostructure—nanoglasses—leads to yet another class of materials potentially with modified properties. Here, evidence is presented that the nanoglass model system Fe90Sc10 exhibits enhanced magnetic properties: it is shown that this nanoglass (prepared by cold compaction of glassy nanospheres) is a ferromagnet at ambient temperature although the isolated nanospheres are paramagnetic. Structural studies reveal that it consists of glassy nanospheres connected by regions with reduced atomic density. The ferromagnetism is explained by the presence of such regions of low atomic density.

Ink-Jet Printed CMOS Electronics from Oxide Semiconductors

Complementary metal oxide semiconductor (CMOS) technology with high transconductance and signal gain is mandatory for practicable digital/analog logic electronics. However, high performance all-oxide CMOS logics are scarcely reported in the literature; specifically, not at all for solution-processed/printed transistors. As a major step toward solution-processed all-oxide electronics, here it is shown that using a highly efficient electrolyte-gating approach one can obtain printed and low-voltage operated oxide CMOS logics with high signal gain (≈21 at a supply voltage of only 1.5 V) and low static power dissipation.

Electrolyte-Gated, High Mobility Inorganic Oxide Transistors from Printed Metal Halides

Inkjet printed and low voltage (≤1 V) driven field-effect transistors (FETs) are prepared from precursor-made In2O3 as the transistor channel and a composite solid polymer electrolyte (CSPE) as the gate dielectric. Printed halide precursors are annealed at different temperatures (300-500 °C); however, the devices that are heated to 400 °C demonstrate the best electrical performance including field-effect mobility as high as 126 cm(2) V(-1) s(-1) and subthreshold slope (68 mV/dec) close to the theoretical limit. These outstanding device characteristics in combination with ease of fabrication, moderate annealing temperatures and low voltage operation comprise an attractive set of parameters for battery compatible and portable electronics.

Room temperature reversible tuning of magnetism of electrolyte-gated La0.75Sr0.25MnO3 nanoparticles

Reversible control of magnetization and Curie temperature (TC) by electrostatic modulation of the surface charge carrier density is presented for the strongly correlated La0.75Sr0.25MnO3 (LSMO) system. The nanoparticulate LSMO was synthesized by spray pyrolysis. A controlled post annealing was carried out to obtain a sharp magnetic transition slightly above room temperature along with favorable surface-to-volume ratios. Resulting nanoporous LSMO was electrostatically charged using a non-aqueous electrolyte with applied voltage limited within the purely capacitive window. The electrostatic charging effect on magnetization was investigated around TC for varying temperatures and applied magnetic fields. The resultant magnetization modulation upon charging is discussed in terms of the reversible electrostatic hole doping.

Electric field induced reversible tuning of resistance of thin gold films

The change in resistance of nanostructured metals with respect to an applied field is believed to be due to a change in carrier concentration and hence a linear variation of resistance with the surface charge is expected. In this article, we propose a different approach to explain the resistance variation based on a change in the effective thickness of the film due to a shift of the electron density profile resulting from the applied surface charge. The change in effective thickness together with its effect on surface scattering of electrons account for the majority of the observed variation in resistance. The thin film geometry with different thicknesses and hence a controlled variation of the surface-to-volume ratio allows a deep quantitative understanding and interpretation of the observed phenomena. The model presented in this work shows that a nominal nonlinear response of the resistance of a metal on electrochemically applied surface charge does not necessarily indicate an onset of a redox reaction.